Elucidating the relationship between red fluorescence and structural dynamics of carbon dots dispersed in different solvents.

The mechanism of intrinsic fluorescence of carbon dots (CDs), the latest nanomaterial from the carbon family, was supposedly deciphered through multiple theories. However, the much sought-after persistent red emission of CDs as a foreseeable consequence of experiments remains elusive prompting the question of whether tuning of the red emission of CDs is a predictable outcome or a serendipitous coincidence. Herein, we tried to decode the same by exploring Alizarin Red S (ARS)-based red emitting CDs in different solvents with wisely chosen analytical tools. The findings are aptly supported by molecular dynamics studies through an experimental intuition-driven model-building approach. Parallel interception of the CDs with powder X-ray diffraction (pXRD) and photophysical spectroscopic studies revealed an important relationship between the solvent and CDs. Tautomerism, a well-known phenomenon with chemical entities, was found to be operative for CDs that greatly influence the Stokes shift and ultimately the fluorescence outcome. Most importantly, pXRD studies established the turbostratism of the CDs where the well-ordered graphitic structure of CDs gets disrupted with solvent molecules. The extent of such disruption is a function of solvent and CD composition that plays a formidable role in obtaining red fluorescence. Thus, for the first time, we demonstrate that the red emission of CDs is related to its structural integrity and if taken care of could be sustained, a tremendously desirable outcome for relevant applications.

Chemically induced crosslinked enhanced emission of carbon polymer dots discerning healthy and cancer cells through pH-dependent tunable photoluminescence.

Chemically induced crosslinked enhanced emission (CEE) of urea and citric acid-derived carbon polymer dot (CPD) nanoparticles is established here with a rare zero linker approach, i.e. without the use of any separate crosslinkers. Such chemical CEE like any chemical reaction was achieved through amide bond formation using carbodiimide chemistry, pointing towards the feasibility of developing a general methodology for their formation through engineering the nanoparticle surface functionality. Exhaustive characterization was done to pinpoint the structure, morphology, and photophysics of the CPDs and concurrently eliminate the possibility of the involvement and interference by molecular fluorophores for the unique optical tuning of the CPDs. The structure-photophysics relation was further restated through theoretical studies involving density functional theory (DFT) that correlated significantly well with the experimental findings. Most interestingly, the CPDs revealed pH responsiveness due to the formation or hydrolysis of amide bonds with acid or base, respectively, which was manifested through a spectacular change in fluorescence emission visible to the naked eye through UV illumination. This distinct pH-dependent photoluminescence properties of CPDs opens up an enormous opportunity for interesting applications, including discriminating normal and cancerous cells, which we demonstrate herein as a proof of concept through in vitro imaging.